S,S-dialkyl-N-substituted phosphoroamidodithionites

ABSTRACT

Compounds of the formula ##STR1## wherein R 1  and R 2  are independently alkyl of 1 to 8 carbon atoms, or alkenyl of 2 to 8 carbon atoms, R 3  is hydrogen or alkyl of 1 to 4 carbon atoms, and R 4  is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, aryl of 6 to 15 carbon atoms optionally substituted with halogen atoms or alkyl groups of 1 to 4 carbon atoms or an acyl group of 2 to 4 carbon atoms, with the proviso that R 3  and R 4  may be joined to form an alkylene radical of 2 to 5 carbon atoms. The compounds possess insecticidal and herbicidal activity.

This is a division of application Ser. No. 565,924, filed Apr. 7, 1975, now U.S. Pat. No. 3,959,271, which in turn, is a division of application Ser. No. 466,433, filed May 2, 1974, now U.S. Pat. No. 3,886,238, which in turn is a division of application Ser. No. 219,559, filed Jan. 20, 1972, now U.S. Pat. 2,832,424.

BACKGROUND OF THE INVENTION

1. Field

The present invention is directed to phosphoroamidodithionites, more particularly S,S-dialkyl-N-mono- and di-substituted phosphoroamidothionites and their use as insecticides and/or herbicides.

2. Description of the Invention

Compounds of the present invention may be represented by the formula ##STR2## wherein R₁ and R₂ are independently alkyl of 1 to 8 carbon atoms, preferably alkyl of 1 to 4 carbon atoms and more preferably alkyl of 3 to 4 carbon atoms, or alkenyl of 2 to 8 carbon atoms, preferably alkenyl of 2 to 4 carbon atoms, R₃ is hydrogen or alkyl of 1 to 4 carbon atoms, R₄ is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms, aryl of 6 to 15 carbon atoms substituted with 0 to 5 halogen atoms of atomic number 9 to 35 or alkyl groups of 1 to 4 carbon atoms, or an acyl group of 2 to 4 carbon atoms, with the proviso that R₃ and R₄ may be joined to form an alkylene radical of 2 to 5 carbon atoms, preferably 4 to 5 carbon atoms.

The aryl groups which R₄ may represent are preferably benzyl or phenyl, either being substituted with 0 to 5 halogen atoms of atomic number 9 to 35 or alkyl groups of 1 to 4 carbon atoms. More preferably, R₄ is phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to 17 or alkyl of 1 to 2 carbon atoms, and still more preferably, phenyl substituted with 0 to 1 chlorine or fluorine atom.

Representative alkyl groups which R₁, R₂, R₃ and R₄ may represent include methyl, ethyl, n-propyl, isopropyl, butyl, t-butyl, etc. Representative alkenyl groups which R₁, R₂ and R₄ may represent include vinyl, allyl, crotyl, etc. R₁ and R₂ may also be pentyl, hexyl, octyl, etc. Preferably R₁ and R₂ will be the same, or will be alkyl. R₄ is preferably alkyl or aryl optionally substituted as the case may be.

Representative aryl groups which R₄ may represent include phenyl, naphthyl, benzyl, o-chlorophenyl, o-fluorophenyl, o-bromophenyl, p-fluorophenyl, m-chlorophenyl, o-methylphenyl, p-butylphenyl, o-butylphenyl, o,p-dichlorophenyl, pentachlorophenyl, o-chloro-p-methylphenyl, o-fluoro-m-chlorophenyl, 2-chloronapthyl, etc.

Representative radicals which R₃ and R₄ joined together with nitrogen may represent include piperidyl, pyrrolidyl and morpholine.

Representative acyl groups which R₄ may represent include acetyl, propionyl and butyryl.

Representative compounds of the present invention include S,S-dimethyl-N-butyl phosphoroamidodithionite, S,S,-dimethyl-N-phenyl phosphoroamidodithionite, S,S-diethyl-N,N-dimethyl phosphoroamidodithionite, S,S-dimethyl-N-acetyl phosphoroamidodithionite, S-methyl-S-ethyl-N-isopropyl phosphoroamidodithionite, S-methyl-S-ethyl-N-vinyl phosphoroamidodithionite, S,S-diethyl-N,N-diethyl phosphoroamidodithionite, S,S-diisopropyl-N-methyl phosphoroamidodithionite, S,S-n-butyl phosphoroamidodithionite, S-methyl-S-hexyl-N-ethyl-N-propionyl phosphoroamidodithionite, S-propyl-S-allyl-N-methyl-N-phenyl phosphoroamidodithionite, S-methyl-S-vinyl-N-methyl phosphoroamidodithionite, S,S-dipropyl-N-2-chlorophenyl phosphoroamidodithionite, S,S-dibutyl-N-2,4-dichlorophenyl phosphoroamidodithionite, S,S-dibutyl-N-2-ethylphenyl phosphoroamidodithionite, S,S-diethyl-N-ethyl-N-2-naphthyl phosphoroamidodithionite, S,S-dibutyl-N-pentachlorophosphoroamidodithionite, S,S-dibutyl-N-2,4-dichloro-3,5-dimethylphenyl phosphoroamidodithionite, S,S-dibutyl-N-piperidyl phosphoroamidodithionite, S,S-dibutyl-N-pyrrolidyl phosphoroamidodithionite, etc.

The compounds of the present invention are prepared by the reaction of an appropriate S,S-dialiphatic hydrocarbyl phosphorus halide with ammonia with a suitable amine or with an appropriate amide according to the following reaction: ##STR3## wherein R₁, R₂, R₃ and R₄ are as indicated above and X is a halogen, preferably chlorine.

Generally, the reaction is accomplished by adding the ammonia or amine slowly to the phosphorus chloride. Preferably an excess, e.g., up to twice the molar amount of ammonia, amide or the amine can be used. The excess reactant acts as a base acceptor to react with the evolved HX and thereby neutralize it. The reaction is preferably carried out in the presence of an inert solvent, such as methylene chloride ether, benzene, hexane, etc. Also a molecular seive is preferably present which serves as a drying agent for the solvent amine. The amount of molecular seive should be enough to assure substantially complete removal of any H₂ O.

When ammonia is reacted with the phosphorus chloride it is generally preferable to dissolve the ammonia in the solvent and then add the phosphorus chloride to the ammonia-solvent mixture. When an amine is used, the solvent is preferably added to the phosphorus chloride and the amine added slowly to the phosphorus chloride-solvent mixture.

The above reaction is preferably carried out at a temperature from -78° to 30° C. Following the reaction, the product can be recovered by conventional means. Thus the reaction mixture may be stripped of solvent, the product washed with water and dried over magnesium sulfate.

The phosphorus chloride is known in the art and can be prepared as for example by the procedure in U.S. Pat. No. 3,210,244. Thus a suitable mercaptan may be reacted with phosphorus trichloride to give the S,S-dialiphatic hydrocarbyl phosphorus chloride. If different alkyl or alkenyl groups are desired, two different mercaptans can be reacted with the phosphorus trichloride.

The present invention can be more fully understood by reference to the following examples.

EXAMPLE 1

Preparation of S,S-di-n-butyl phosphoroamidodithionite

Ammonia (large excess based on the amount of S,S-dibutyl phosphorus chloride) was dissolved in methylene dichloride, cooled to dry ice temperature. A small number of molecular sieves were added. S,S-dibutyl phosphorus chloride, 6.5 g. (0.03 mole), was then added slowly. A solid white precipitate resulted. The reaction mixture was slowly warmed up to room temperature and left standing approximately 48 hours. The white solid was removed and the remaining solution stripped to obtain an oil having the following analysis:

    ______________________________________                                                      Calculated                                                                               Found                                                   ______________________________________                                         N          %       6.2         5.5                                             ______________________________________                                    

EXAMPLE 2

Preparation of S,S-di-n-butyl-N,N-diethyl phosphoroamidodithionite

100 ml. of methylene dichloride plus a small amount of molecular sieves were mixed with 13.05 g. of S,S-di-n-butyl phosphorus chloride. Diethyl amine (7.8 g.) was added slowly. The resulting slurry was allowed to stand for approximately 24 hours. The resulting mixture was filtered and stripped to obtain a colorless oil which on chemical analysis showed:

    ______________________________________                                                      Calculated                                                                               Found                                                   ______________________________________                                         S          %       22.8        21.7                                            P          %       11.01       11.8                                            ______________________________________                                    

EXAMPLE 3

Preparation of S,S-di-n-butyl-N-pyrrolidyl phosphoroamidodithionite

5.84 g. (0.024 mole) of S,S-di-n-butyl phosphorus chloride was dissolved in approximately 150 ml. of methylene dichloride. A small number of molecular sieves were added. Piperidine, 4.06 g. (0.05 mole) was added slowly. The reaction mixture was cooled in an ice bath during the reaction. The reaction mixture was permitted to stand overnight after which it was filtered and evaporated down to obtain a yellow oil which was then dissolved in methylene dichloride, washed twice with water and dried over magnesium sulfate. After isolation, the chemical analysis showed:

    ______________________________________                                                      Calculated                                                                               Found                                                   ______________________________________                                         S          %       21.8        22.1                                            P          %       10.6        10.4                                            ______________________________________                                    

EXAMPLE 4

Preparation of S,S-di-n-butyl-N-acetyl phosphoroamidodithionite

Under a nitrogen atmosphere, 50 ml. of diethyl ether was dried over several molecular sieves. Then, 9.15 g. (0.0373 mole) of S,S-di-n-butyl phosphorus chloride was added to the dry ether. Next, 2.21 g. (0.0373 mole) of acetamide was added and the reaction mixture turned cloudy. Triethylamine, 3.78 g. (0.0373 mole) was added dropwise. A white precipitate formed, and the reaction mixture was stirred for 1 hour at ambient temperature. After warming, the reaction mixture was stirred for 24 hours.

The white precipitate was removed by filtration. The resulting solution slowly formed two layers. After 30 days the layers were separated. The upper layer weighed 5.30 grams. Analysis:

    ______________________________________                                                      Calculated                                                                               Found                                                   ______________________________________                                         S          %       24.0        26.3                                            P          %       11.6        13.8                                            ______________________________________                                    

The NMR spectra was consistent with the assigned structure. The infrared spectra had adsorption peaks at 5.85, 6.85, 7.25, 7.85, 8.1, 8.3 and 13.4 microns.

Other compounds of the present invention were prepared substantially as described above and are reported in Table I. All of the compounds are oils.

                                      TABLE I                                      __________________________________________________________________________                        Elemental Analysis - %                                      Ex.                S         P         Halogen                                 No.     Compound   Calculated                                                                           Found                                                                              Calculated                                                                           Found                                                                              Calculated                                                                           Found                             __________________________________________________________________________      5 S,S-n-butyl-N,N-di-n-propyl                                                                    20.7  20.7                                                                               10.0  10.0                                                                               --    --                                   phosphoroamidodithionite                                                     6 S,S-di-n-butyl-N,N-dimethyl                                                                    25.3  25.1                                                                               12.2  11.8                                                                               --    --                                   phosphoroamidodithionite                                                     7 S,S-di-n-butyl-N-methyl                                                                        5.8*  5.3*                                                                               --    --  --    --                                   phosphoroamidodithionite                                                     8 S,S-di-n-butyl-N,N-di-n-butyl                                                                  19.0  19.0                                                                               9.2   8.8 --    --                                   phosphoroamidodithionite                                                     9 S,S-diisopropyl-N,N-diethyl                                                                    --    --  12.2  11.8                                                                               --    --                                   phosphoroamidodithionite                                                    10 S,S-diisopropyl-N,N-di-N-propyl                                                                22.8  22.3                                                                               11.0  10.6                                                                               --    --                                   phosphoroamidodithionite                                                    11 S,S-di-n-butyl-N-4-chlorophenyl                                                                10.6**                                                                               10.5**                                                                             --    --  --    --                                   phosphoroamidodithionite                                                    12 S,S-di-n-butyl-N-2-fluorophenyl                                                                6.0** 6.2**                                                                              --    --  --    --                                   phosphoroamidodithionite                                                    13 S,S-diisopropyl-N-4-chlorophenyl                                                               11.5**                                                                               9.8*                                                                               10.1  9.2 --    --                                   phosphoroamidodithionite                                                    14 S,S-diisopropyl-N-2-fluorophenyl                                                               22.0  21.8                                                                               11.6  11.0                                                                               --    --                                   phosphoroamidodithionite                                                    15 S,S-diisopropyl-N,N-di-n-butyl                                                                 20.7  18.6                                                                               10.0  9.2 --    --                                   phosphoroamidodithionite                                                    16 S,S-diisopropyl phosphoroamido-                                                                7.1*  6.6*                                                                               --    --  --    --                                   dithionite                                                                  17 S,S-diisopropyl-N-methyl                                                                       6.6*  6.1*                                                                               --    --  --    --                                   phosphoroamidodithionite                                                    18 S,S-diisopropyl-N-ethyl                                                                        28.5  27.0                                                                               13.7  12.8                                                                               --    --                                   phosphoroamidodithionite                                                    19 S,S-diisopropyl-N-n-butyl                                                                      25.3  23.8                                                                               12.2  11.6                                                                               --    --                                   phosphoroamidodithionite                                                    20 S,S-diethyl-N,N-diethyl                                                                        28.5  25.6                                                                               13.8  13.0                                                                               --    --                                   phosphoroamidodithionite                                                    21 S,S-diethyl-N,N-di-n-butyl                                                                     28.5  25.4                                                                               13.8  12.1                                                                               --    --                                   phosphoroamidodithionite                                                    22 S,S-diethyl-N,N-dimethyl                                                                       32.5  30.0                                                                               15.7  14.9                                                                               --    --                                   phosphoroamidodithionite                                                    23 S,S-diethyl-N-ethyl                                                                            32.5  29.6                                                                               15.7  14.6                                                                               --    --                                   phosphoroamidodithionite                                                    24 S,S-di-n-butyl-N-benzyl                                                                        20.4  18.4                                                                               9.8   9.1 --    --                                   phosphoroamidodithionite                                                    25 S,S-di-n-butyl-N-allyl                                                                         24.2  21.9                                                                               11.7  10.6                                                                               --    --                                   phosphoroamidodithionite                                                    26 S,S-di-n-propyl-N,N-diethyl                                                                    25.3  23.6                                                                               12.2  11.3                                                                               --    --                                   phosphoroamidodithionite                                                    27 S,S-di-n-propyl-N-n-butyl                                                                      25.3  25.1                                                                               12.2  11.3                                                                               --    --                                   phosphoroamidodithionite                                                    28 S,S-di-n-propyl-N,N-dimethyl                                                                   28.5  27.5                                                                               13.8  12.5                                                                               --    --                                   phosphoroamidodithionite                                                    29 S,S-di-n-propyl-N-methyl                                                                       30.4  30.3                                                                               14.6  14.8                                                                               --    --                                   phosphoroamidodithionite                                                    30 S,S-di-n-propyl-N-piperidyl                                                                    24.2  21.9                                                                               11.7  10.6                                                                               --    --                                   phosphoroamidodithionite                                                    31 S,S-di-n-propyl-N,N-di-n-propyl                                                                22.8  21.1                                                                               11.0  10.4                                                                               --    --                                   phosphoroamidodithionite                                                    32 S,S-di-n-propyl-N-benzyl                                                                       22.3  22.5                                                                               10.8  10.4                                                                               --    --                                   phosphoroamidodithionite                                                    33 S,S-di-n-propyl-N-allyl                                                                        27.1  23.9                                                                               13.1  13.0                                                                               --    --                                   phosphoroamidodithionite                                                    34 S,S-di-n-propyl-N-2-fluorophenyl                                                               22.0  20.0                                                                               10.6  10.5                                                                               --    --                                   phosphoroamidodithionite                                                    35 S,S-di-n-propyl-N-ethyl                                                                        28.5  29.0                                                                               13.8  13.6                                                                               --    --                                   phosphoroamidodithionite                                                    36 S,S-di-n-propyl-N-n-butyl                                                                      20.7  20.5                                                                               10.0  10.0                                                                               --    --                                   phosphoroamidodithionite                                                    37 S,S-di-n-octyl-N-methyl                                                                        18.2  17.6                                                                               8.8   8.2 --    --                                   phosphoroamidodithionite                                                    38 S,S-di-n-octyl-N-piperidyl                                                                     15.8  14.8                                                                               7.6   7.2 --    --                                   phosphoroamidodithionite                                                    39 S,S-di-n-octyl-N-butyl                                                                         16.3  15.0                                                                               7.9   7.7 --    --                                   phosphoroamidodithionite                                                    40 S,S-di-n-propyl-N-acetyl-N-                                                                    20.3  21.3                                                                               9.9   10.4                                                                               --    --                                   phenyl phosphoroamidodithionite                                             41 S,S-di-n-propyl-N-acetyl                                                                       26.8  26.3                                                                               13.0  12.1                                                                               --    --                                   phosphoroamidodithionite                                                    42 S,S-di-i-propyl-N-butyryl                                                                      24.0  23.6                                                                               11.6  11.5                                                                               --    --                                   phosphoroamidodithionite                                                    43 S,S-di-i-propyl-N-acetyl                                                                       --    --  12.9  11.8                                                                               0.0** 0.19**                               phosphoroamidodithionite                                                    44 S,S-di-n-butyl-N-propionyl                                                                     --    --  10.5  10.9                                                                               4.7*  3.2*                                 phosphoroamidodithionite                                                    __________________________________________________________________________      *nitrogen                                                                      **halogen                                                                

The compounds of the present invention are, in general, herbicidal in both pre- and post-emergence applications. For pre-emergence control of undesirable vegetation these compounds will be applied in herbicidal quantities to the environment, e.g., soil infested with seeds and/or seedlings of such vegetation. Such application will inhibit the growth of or kill the seeds, germinating seeds and seedlings. For post-emergence applications the compounds of the present invention will be applied directly to the foliage and other plant parts. Generally they are effective against weed grasses as well as broadleaved weeds. Some may be selective with respect to type of application and/or type of weed.

Pre- and post-emergence herbicidal tests on representative compounds of this invention were made using the following methods:

PRE-EMERGENCE TEST

An acetone solution of the test compound was prepared by mixing 750 mg. compound, 220 mg. of a nonionic surfactant and 25 ml. of acetone. This solution was added to approximately 125 ml. of water containing 156 mg. of surfactant.

Seeds of the test vegetation were planted in a pot of soil and the compound solution was sprayed uniformly onto the soil surface at a dose of 100 micrograms per cm². The pot was watered and placed in a greenhouse. The pot was watered intermittently and was observed for seedling emergence, health of emerging seedlings, etc. for a 3-week period. At the end of this period the herbicidal effectiveness of the compound was rated based on the physiological observations. A 0 to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.

POST-EMERGENCE TEST

The test compound was formulated in the same manner as described above for the pre-emergence test. The concentration of the compound in this formulation was 5000 ppm. This formulation was uniformly sprayed on 2 replicate pots of 24-day-old plants (approximately 15 to 25 plants per pot) at a dose of 100 micrograms per cm². After the plants had dried, they were placed in a greenhouse and then watered intermittently at their bases as needed. The plants were observed periodically for phytotoxic effects and physiological and morphological responses to the treatment. After 3 weeks the herbicidal effectiveness of the compound was rated based on these observations. A 0 to 100 scale was used; 0 representing no phytotoxicity, 100 representing complete kill.

The results of these tests appear in Table II.

                                      TABLE II                                     __________________________________________________________________________                       Herbicidal Effectiveness - %                                 Compound          0    W    C     M     P     L                                __________________________________________________________________________     S,S-di-n-butyl-N,N-diethyl                                                     /93                    93/85                                                                               100/100                                            /100                                    100/100                                                                              100/100                          phosphoroamidodithionite                                                       S,S-n-butyl-N,N-di-n-propyl                                                    /100                                                                           /100                                                                           /100                                                                           /100                                                                           /100                                                                           /100                                                                           phosphoroamidodithionite                                                       S,S-di-n-butyl-N,N-dimethyl                                                    /85                                                                            /85                                                                            /80                                                                            /95                                                                            /85                                                                            /65                                                                            phosphoroamidodithionite                                                       S,S-di-n-butyl phosphoroamido-                                                                    65/85                                                       /90               90/- 80/100                                                                              --                                                 /75                                                                            dithionite                                                                     S,S-di-n-butyl-N-methyl                                                        /95               70/80                                                                               100/75                                                                              95/100                                                                               90/-  90/80                                  phosphoroamidodithionite                                                       S,S-di-n-butyl-N,N-di-n-butyl                                                  /90                                                                            /75               --                                                           /75               --   --                                                      phosphoroamidodithionite                                                       S,S-diisopropyl-N,N-diethyl                                                                      --                                                           /70               --                                                           /90               --   --                                                      phosphoroamidodithionite                                                       S,S-diisopropyl-N,N-di-n-propyl                                                                  --                                                           /70               --                                                           /60                                                                            /55               --                                                           phosphoroamidodithionite                                                       S,S-di-n-butyl-N-2-fluorophenyl                                                                  --   --   --                                                 /80                                                                            /95                                                                            /55                                                                            phosphoroamidodithionite                                                       S,S-diisopropyl-N,N-di-n-butyl                                                 /100              --   --   --                                                                   75/-                                                         /70                                                                            phosphoroamidodithionite                                                       S,S-diisopropyl phosphoroamido-                                                                  --   --   --    80/-  70/-  --                               dithionite                                                                     S,S-diisopropyl-N-methyl                                                                         --   --   --    70/-  80/-  --                               phosphoroamidodithionite                                                       S,S-di-n-butyl-N-pyrrolidyl                                                                       95/100                                                                             70/75                                                                               100/-  95/100                                      /100              90/90                                                        phosphoroamidodithionite                                                       S,S-diisopropyl-N-ethyl                                                                          --   100/-                                                                               --    --    --    --                               phosphoroamidodithionite                                                       S,S-diisopropyl-N-n-butyl                                                                        100/-                                                                               100/-                                                                               80/-                                               /90                                                                            /60                                                                            /60                                                                            phosphoroamidodithionite                                                       S,S-di-n-octyl-N-methyl                                                                          --   --   --                                                 /70                                                                            /60               --                                                           phosphoroamidodithionite                                                       S,S-di-n-octyl-N-piperidyl                                                                       --   --   75/-  --    --    --                               phosphoroamidodithionite                                                       S,S-diethyl-N,N-diethyl                                                        /90                                                                            /90               --                                                           /95                                                                            /95                                                                            /100                                                                           phosphoroamidodithionite                                                       S,S-diethyl-N,N-di-n-butyl                                                     /80                                                                            /80                                                                            /90                                                                            /100                                                                           /95                                                                            /95                                                                            phosphoroamidodithionite                                                       S,S-diethyl-N,N-dimethyl                                                                         --                                                           /70                                                                            /80                                                                            /80                                                                            /70                                                                            /100                                                                           phosphoroamidodithionite                                                       S,S-diethyl-N-ethyl                                                                              --   --   80/75                                              /100                                                                           /85                                                                            /100                                                                           phosphoroamidodithionite                                                       S,S-di-n-butyl-N-benzyl                                                        /95                                                                            /90               100/90                                                                               95/100                                                                              95/100                                                                               95/100                                      phosphoroamidodithionite                                                       S,S-di-n-propyl-N-acetyl                                                                         100/-                                                                               100/-                                                                               100/- 100/- 100/- 100/100                          phosphoroamidodithionite                                                       S,S-di-i-propyl-N-butyryl                                                                        --   --   --    85/-  --    --                               phosphoroamidodithionite                                                       S,S-di-i-propyl-N-acetyl                                                                         --   --   --    100/- 90/-  85/-                             phosphoroamidodithionite                                                       S,S-di-n-propyl-N,N-diethyl                                                    /95                                                                            /95                                                                            /90                                                                            /100              100/100                                                      phosphoroamidodithionite                                                       S,S-di-n-propyl-N-n-butyl                                                      /100                                                                           /100                                                                           /95                                                                            /100                                                                           /100                                                                           /100                                                                           phosphoroamidodithionite                                                       S,S-di-n-propyl-N,N-dimethyl                                                                     --                                                           /75               --                                                           /80                                                                            /95                                                                            /100                                                                           phosphoroamidodithionite                                                       S,S-di-n-propyl-N-piperidyl                                                    /85                                                                            /80               100/80                                                       /100               95/100                                                                              95/100                                                 phosphoroamidodithionite                                                       S,S-di-n-propyl-N-methyl                                                                         100/-                                                                               80/85                                                                               100/90                                                                               100/100                                                                              100/100                                                                              100/100                          phosphoroamidodithionite                                                       S,S-di-n-propyl-N,N-di-n-propyl                                                /90                                                                            /95               100/95                                                       /100                                                                           /100               90/100                                                      phosphoroamidodithionite                                                       S,S-di-n-propyl-N-benzyl                                                                         --   70/-`                                                                               100/- 100/- 100/- 100/75                           phosphoroamidodithionite                                                       S,S-di-n-propyl-N-allyl                                                                          100/-                                                                               --   80/-  --    --    95/-                             phosphoroamidodithionite                                                       S,S-di-n-propyl-N-ethyl                                                                          95/- --   --    --    90/-  --                               phosphoroamidodithionite                                                       S,S-di-n-butyl-N-propionyl                                                                       --                                                           /75               --   80/90                                                                               80/-  --                                           phosphoroamidodithionite                                                       S,S-di-n-butyl-N-acetyl                                                        /100                                                                           /100              100/100                                                                             100/100                                                                              70/100                                                                               80/100                                      phosphoroamidodithionite                                                       __________________________________________________________________________      O = Wild Oats (Avena fatua)                                                    W = Watergrass (Echinochloa crusgalli)                                         C = Crabgrass (Digitaria sanguinalis)                                          M = Mustard (Brassica arvensis)                                                P = Pigweed (Amaranthus retroflexus)                                           L = Lamsquarter (Chenopodium album)                                      

The amount of compound administered will vary with the particular plant part or plant growth medium which is to be contacted, the general location of application, i.e., sheltered areas such as greenhouses as compared to exposed areas such as fields, as well as the desired type of control. For pre-emergent control of most plants dosages in the range of about 0.5 to 20 lbs. per acre will be used. Such administration will give a concentration of about 2 to 80 ppm. compound distributed throughout 0.1 acre-foot. For post-emergence application, such as foliar spray application, compositions containing about 0.5 to 8 lbs. compound per 100 gal. spray will be used. Such application is equivalent to about 0.5 to 20 lbs. compound per acre.

The herbicidal compositions of this invention comprise a herbicidal amount of one or more of the above described compounds intimately admixed with a biologically inert carrier. The carrier may be a liquid diluent such as water or acetone or a solid. The solid may be in the form of dust powder or granules. These compositions will also usually contain adjuvants such as a wetting or dispersing agent to facilitate their penetration into the plant growth media or plant tissue and generally enhance their effectiveness. These compositions may also contain other pesticides, stabilizers, conditioners, fillers and the like.

The compounds of the present invention also possess insecticidal activity. Representative compounds were tested as follows to illustrate the insecticidal properties. The test results are reported in Table III.

TEST PROCEDURES

Two-spotted Mites (Tetranychus urticae):

An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 100 ppm. Pinto bean leaves which were infested with mites were dipped in the toxicant solution. Mortality readings were taken after 24 hours.

Two-spotted Mite Eggs (Tetranychus urticae):

An Acetone solution of the candidate toxicant was prepared containing a small amount of a nonionic surfactant. The acetone solution was diluted with water to give a 100 ppm solution. A primary leaf from Pinto beans which had been infested with mites 48 hours before and consequently contained mite eggs was immersed in the toxicant solution and then allowed to dry at room temperature for seven days at 85° F. On the eighth day the egg mortality was rated on a scale of 0 to 11; 0 representative no kill, 11 representing 100% kill.

Aphids (Aphis gossypii Glover):

An acetone solution of the candidate toxicant containing a small amount of nonionic emulsifier was diluted with water to 30 ppm. Cucumber leaves infested with the cotton aphids were dipped in the toxicant solution. Mortality readings were then taken after 24 hours.

                                      TABLE III                                    __________________________________________________________________________                        % Control                                                                             Two-spotted                                                             Two-spotted                                                                           Mites                                                Compound           Mites  Eggs   Aphids                                        __________________________________________________________________________     S,S-di-n-butyl-N,N-dimethyl                                                                        70     96    --                                            phosphoroamidodithionite                                                       S,S-n-butyl-N,N-di-n-propyl                                                                       --     100    --                                            phosphoroamidodithionite                                                       S,S-di-n-butyl     --      98    --                                            phosphoroamidodithionite                                                       S,S-di-n-butyl-N-methyl                                                                            99    --      99                                           phosphoroamidodithionite                                                       S,S-di-n-butyl-N-2-fluorophenyl                                                                   --      96    --                                            phosphoroamidodithionite                                                       S,S-diisopropyl-N-methyl                                                                           98    --     --                                            phosphoroamidodithionite                                                       S,S-diisopropyl-N-ethyl                                                                           100    --      96                                           phosphoroamidodithionite                                                       S,S-diethyl-N-ethyl                                                                                85    --     --                                            phosphoroamidodithionite                                                       S,S-di-n-propyl-N,N-diethyl                                                                        97*   --     100                                           phosphoroamidodithionite                                                       S,S-di-n-propyl-N,N-dimethyl                                                                      100    --     100                                           phosphoroamidodithionite                                                       S,S-di-n-propyl-N-methyl                                                                          100    90     100                                           phosphoroamidodithionite                                                       S,S-di-n-propyl-N-piperidyl                                                                       100    96     --                                            phosphoroamidodithionite                                                       S,S-di-n-propyl-N,N-di-n-propyl                                                                   99     99     --                                            phosphoroamidodithionite                                                       S,S-di-n-propyl-N-benzyl                                                                          100    99     --                                            phoshoroamidodithionite                                                        S,S-di-n-propyl-N-allyl                                                                           99     --     --                                            phoshoroamidodithionite                                                        S,S-di-n-propyl-N-2-fluorophenyl                                                                  70     100    --                                            phosphoroamidodithionite                                                       S,S-di-n-propyl-N-ethyl                                                                           100    90     94                                            phosphoroamidodithionite                                                       S,S-di-n-butyl-N-acetyl                                                                           96     96     94                                            phosphoroamidodithionite                                                       S,S-di-n-butyl-N-propionyl                                                                        --     98     --                                            phosphoroamidodithionite                                                       S,S-di-n-propyl-N-acetyl                                                                          100    100    100                                           phosphoroamidodithionite                                                       S,S-di-n-propyl-N-acetyl-N-phenyl                                                                 100    --     96                                            phosphoroamidodithionite                                                       __________________________________________________________________________      *40 ppm                                                                  

In general, the preferred compounds for use as insecticides are those wherein R₁ and R₂ are individually propyl or butyl, R₃ is hydrogen, methyl, ethyl or propyl and R₄ is hydrogen, methyl, ethyl, propyl or fluorophenyl; or benzyl or allyl when R₁ and R₂ are propyl.

In addition to the specific formulations and application techniques described above, one or more of the compound derivatives of the invention may be applied in other liquid or solid formulations to the insects, their environment, or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxic amount of one or more carbamate derivatives and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as clay, talc, sawdust and the like may be used in such formulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other compatible pesticides, plant growth regulators, fillers, stabilizers, attractants and the like.

The concentration of the active ingredient to be used with inert carriers, either solid or liquid carriers, will be dependent upon many factors, such as the particular carbamate compound which is used, the carrier in or upon which it is incorporated, the method and conditions of application, the insect species to be controlled, etc., the proper consideration of these factors being within the skill of these versed in the art. In general, the toxic ingredients of this invention will be effective in concentrations from about 0.0001 percent by weight to as high as 90 percent by weight or higher. Economically, of course, it is desirable to use lower concentrations of this active ingredient. Thus, it is usually desirable to use less than 20 percent by weight of the active ingredient in a particular composition.

The terms "insecticide" and "insect" as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term "insect" is used not only to include small invertebrate animals belonging to the class Insecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.

Some of the compounds of the present invention are also useful in the control of nematodes and algae, for example Euglena.

As will be evident to those skilled in the art, various modifications on this invention can be made or followed, in the light of the foregoing disclosure and discussion, without departing from the spirit or scope of the disclosure or from the scope of the following claims. 

I claim:
 1. A compound of the formula ##STR4## wherein R₁ and R₂ are independently alkyl of 1 to 8 carbon atoms or alkenyl of 2 to 8 carbon atoms, R₃ is hydrogen or alkyl of 1 to 4 carbon atoms and R₄ is alkenyl of 2 to 4 carbon atoms or aryl of 6 to 15 carbon atoms substituted with 0 to 5 halogen atoms of atomic number 9 to 35 or alkyl groups of 1 to 4 carbon atoms.
 2. Compound of claim 1 wherein R₁ and R₂ are independently alkyl of 1 to 4 carbon atoms.
 3. Compound of claim 1 wherein R₁ and R₂ are independently alkyl of 3 to 4 carbon atoms.
 4. Compound of claim 1 wherein R₄ is phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to 35 or alkyl of 1 to 2 carbon atoms.
 5. Compound of claim 1 wherein R₁ and R₂ are the same and are alkyl of 1 to 4 carbon atoms, R₃ is hydrogen or alkyl of 1 to 4 carbon atoms, R₄ is phenyl substituted with 0 to 1 chlorine or fluorine atom.
 6. Compound of claim 1 wherein R₄ is alkenyl of 2 to 4 carbon atoms. 